153759-58-1 5-溴-3-叔丁基-2-羟基苯甲醛

运输信息：常温运输。危险描述：非危险化学品（但GHS分类显示其具有急性毒性（口服、皮肤、吸入）、皮肤刺激、严重眼损伤、呼吸道刺激等危害，需注意防护）。

主要用于化学合成领域。

化学合成

合成路线 1（1. 合成：153759-58-1）

产率：73% 合成条件：With bromine In acetic acid at 20℃; for 3 h; 实验步骤：步骤2：5-溴-3-（叔丁基）-2-羟基苯甲醛（7b）向化合物7a（3.0g，17mmol）的AcOH（15mL）溶液中加入Br₂（2.95g，18mmol）。在室温下滴加并将混合物搅拌3小时。TLC（PE：EA = 50：1）显示反应完成。将反应混合物用水溶液淬灭。用NaHSO₃（50mL）萃取，用Et₂O萃取。减压浓缩有机层，得到粗化合物7b（3.2g，73％），为白色固体。 参考文献：[1] Journal of Medicinal Chemistry, 2013, vol. 56, #20, p. 8163-8182 [2] Advanced Synthesis and Catalysis, 2009, vol. 351, #9, p. 1325-1332 [3] Inorganic Chemistry, 2017, vol. 56, #20, p. 12357-12361 [4] Chemistry - A European Journal, 2006, vol. 12, #2, p. 576-583 [5] European Journal of Organic Chemistry, 2001, #24, p. 4639-4649 [6] Tetrahedron Asymmetry, 2007, vol. 18, #17, p. 2016-2020 [7] Chemical Communications, 2014, vol. 50, #58, p. 7870-7873 [8] European Journal of Inorganic Chemistry, 2013, #24, p. 4228-4233 [9] Dalton Transactions, 2017, vol. 46, #29, p. 9491-9497 [10] Russian Journal of Organic Chemistry, 2014, vol. 50, #2, p. 191-199 [11] Zh. Org. Khim., 2014, vol. 50, #2, p. 201-208,8 [12] Patent: EP2511263, 2012, A1. Location in patent: Page/Page column 28 [13] Patent: WO2012/139775, 2012, A1. Location in patent: Page/Page column 40 [14] Patent: WO2014/15054, 2014, A1. Location in patent: Page/Page column 215 [15] Journal of Medicinal Chemistry, 2007, vol. 50, #7, p. 1658-1667 [16] Tetrahedron, 2004, vol. 60, #46 SPEC. ISS., p. 10461-10468 [17] Journal of the American Chemical Society, 2005, vol. 127, #6, p. 1854-1869 [18] Chemical Communications, 2003, #15, p. 1860-1861 [19] Patent: US2010/21423, 2010, A1 [20] Patent: US2010/81658, 2010, A1. Location in patent: Page/Page column 27-28 [21] Patent: WO2010/122082, 2010, A1. Location in patent: Page/Page column 36 [22] Polymer, 2010, vol. 51, #5, p. 994-997 [23] ChemSusChem, 2014, vol. 7, #8, p. 2110-2114 [24] Tetrahedron Letters, 2016, vol. 57, #50, p. 5644-5648 [25] Patent: US2010/297073, 2010, A1. Location in patent: Page/Page column 18

路线2：5-溴-3-叔丁基-2-羟基苯甲醛（7b）的合成

向3-叔丁基-2-羟基苯甲醛（7a，3.0g，17mmol）的乙酸（15mL）溶液中缓慢加入溴（2.95g，18mmol）。反应在室温下进行，滴加完毕后继续搅拌3小时。通过薄层色谱（TLC，展开剂比例石油醚：乙酸乙酯=50：1）监测反应进程，确认反应完成。反应混合物用水淬灭后，用亚硫酸氢钠溶液（50mL）洗涤，再用乙醚萃取。合并有机层，减压浓缩，得到粗产物5-溴-3-叔丁基-2-羟基苯甲醛（7b，3.2g，收率73%），为白色固体。 参考文献：[1] Journal of Medicinal Chemistry, 2013, vol. 56, #20, p. 8163-8182 [2] Advanced Synthesis and Catalysis, 2009, vol. 351, #9, p. 1325-1332 [3] Inorganic Chemistry, 2017, vol. 56, #20, p. 12357-12361 [4] Chemistry - A European Journal, 2006, vol. 12, #2, p. 576-583 [5] European Journal of Organic Chemistry, 2001, #24, p. 4639-4649